Quantification of bisphenol A, 353-nonylphenol and their chlorinated derivatives in drinking water treatment plants

Bisphenol A (BPA) and nonylphenols (NP) are of major concern to public health due to their high potential for human exposure and to their demonstrated toxicity (endocrine disruptor effect). A limited number of studies have shown that BPA and NP are present in drinking water. The chlorinated derivatives that may be formed during the chlorination step in drinking water treatment plants (DWTP) exhibit a higher level of estrogenic activity than their parent compounds. The aim of this study was to investigate BPA, 353NP, and their chlorinated derivative concentrations using an accurate and reproducible method of quantification. This method was applied to both surface and treated water samples from eight French DWTPs producing from surface water. Solid-phase extraction followed by liquid chromatography?Ctandem mass spectrometry was developed in order to quantify target compounds from water samples. The limits of detection ranged from 0.3 to 2.3?ng/L for BPA and chlorinated BPA and from 1.4 to 63.0?ng/L for 353NP and chlorinated 353NP. BPA and 353NP were found in most analyzed water samples, at a level ranging from 2.0 to 29.7?ng/L and from 0 to 124.9?ng/L, respectively. In most of DWTPs a decrease of BPA and 353NP was observed between surface water and treated water (36.6 to 78.9?% and 2.2 to 100.0?% for BPA and 353NP, respectively). Neither chlorinated BPA nor chlorinated 353NP was detected. Even though BPA and 353NP have been largely removed in the DWTPs studied, they have not been completely eliminated, and drinking water may consequently remain a source of human exposure.     

Application of ozone for the removal of bisphenol A from water and wastewater – A review

The extensive use of Bisphenol A (BPA) in the plastics industry has led to increasing reports of its presence in the aquatic environment, with concentrations of ng L^?1 to μg L^?1. Various advanced oxidation processes, including ozonation, have been shown to effectively degrade BPA. This paper reviews the current advancements in using ozone to remove BPA from water and wastewater.Most of the published work on the oxidation of BPA by ozone has focused on the efficiency of BPA removal in terms of the disappearance of BPA, and the effect of various operational parameters such as ozone feed rate, contact time and pH; some information is available on the estrogenic activity of the treated water. Due to increasing operational reliability and cost effectiveness, there is great potential for industrial scale application of ozone for the treatment of BPA. However, there is a significant lack of information on the formation of oxidation by-products and their toxicities, particularly in more complex matrices such as wastewater, and further investigation is needed for a better understanding of the environmental fate of BPA.     

微滤膜与活性炭联用工艺去除富营养化水源水中藻类

湖泊及水库含藻水问题带有一定的普遍性,处理技术复杂,难度较大。因此,除藻技术的提高和发展显得越来越紧迫。膜处理技术在给水中的应用是水处理技术的重大突破,正逐渐成为21世纪水处理技术中最有发展前途的技术。本文以继承和吸收成熟技术,并将其工程化,以便及时解决具体问题为原则,根据国内外最新水质标准要求,提出了微滤膜与活性炭联用的除藻新上艺,并对除藻工艺方案确定原则、研究内容和目标,以及除藻工艺方案设计进行了说细分析说明。本文认为微滤膜技术在我国供水行业推广已经具备了较好的条件,在不断积累经验的基础上可以达到大规模工程应用。应用微滤膜与活性炭联用工艺解决富营养化水源水中藻类问题在技术上是成熟的,在经济上是可行的。     

Catalytic wet air oxidation of bisphenol A solution in a batch-recycle trickle-bed reactor over titanate nanotube-based catalysts

Catalytic wet air oxidation (CWAO) is classified as an advanced oxidation process, which proved to be highly efficient for the removal of emerging organic pollutant bisphenol A (BPA) from water. In this study, BPA was successfully removed in a batch-recycle trickle-bed reactor over bare titanate nanotube-based catalysts at very short space time of 0.6 min g_CAT?g^?1. The as-prepared titanate nanotubes, which underwent heat treatment at 600 °C, showed high activity for the removal of aqueous BPA. Liquid-phase recycling (5- or 10-fold recycle) enabled complete BPA conversion already at 200 °C, together with high conversion of total organic carbon (TOC), i.e., 73 and 98 %, respectively. The catalyst was chemically stable in the given range of operating conditions for 189 h on stream.     

高效聚合氯化铝对超滤膜污染影响的中试研究

针对某水厂以超滤为核心的短流程水处理工艺,在通过聚氯乙烯(PVC)超滤膜之前选择不同投加量(5、10、15和20 mg/L)的高效聚合氯化铝(HPAC)对长江下游原水进行混凝处理。通过跨膜压差(TMP)增长趋势、CODMn的去除率以及混凝后的水质,可知HPAC的最优投加量为15 mg/L。在此投加量下,运用体积排阻色谱法分析原水、膜前水、膜后水中各相对分子质量有机物的变化,可以发现混凝去除有机物的效果要优于超滤截留的。继而将HPAC与另外4种常用混凝剂:硫酸铝(分析纯)、氯化铁(化学纯)、聚合氯化铝(PAC)、聚合硫酸铁进行对比,结果表明,在它们各自最优投加量下,HPAC能够更有效地减缓超滤膜TMP的增长率,从而降低膜污染。因此,认为HPAC是与PVC超滤合金膜契合效果最佳的混凝剂。     

Interaction of bisphenol A with dissolved organic matter in extractive and adsorptive removal processes

The fate of endocrine disrupting chemicals (EDCs) in natural and engineered systems is complicated due to their interactions with various water constituents. This study investigated the interaction of bisphenol A (BPA) with dissolved organic matter (DOM) and colloids present in surface water and secondary effluent as well as its adsorptive removal by powdered activated carbons. The solid phase micro-extraction (SPME) method followed by thermal desorption and gas chromatography-mass spectrometry (GC-MS) was utilized for determining the distribution of BPA molecules in water. The BPA removal by SPME decreased with the increased DOM content, where the formation of BPA-DOM complexes in an aqueous matrix was responsible for the reduced extraction of BPA. Colloidal particles in water samples sorbed BPA leading to the marked reduction of liquid phase BPA. BPA-DOM complexes had a negative impact on the adsorptive removal of BPA by powered activated carbons. The complex formation was characterized based on Fourier transform infrared (FTIR) and ultraviolet-visible (UV-Vis) spectroscopy, along with the calculation of molecular interactions between BPA and functional groups in DOM. It was found that the hydrogen bonding between DOM and BPA would be preferred over aromatic interactions. A pseudo-equilibrium molecular coordination model for the complexation between a BPA molecule and a hydroxyl group of the DOM was developed, which enabled estimation of the maximum sorption site and complex formation constant as well as prediction of organic complexes at various DOM levels.     

Effect of inorganic and organic solutes on zero-valent aluminum-activated hydrogen peroxide and persulfate oxidation of bisphenol A

The effect of varying inorganic (chloride, nitrate, sulfate, and phosphate) and organic (represented by humic acid) solutes on the removal of aqueous micropollutant bisphenol A (BPA; 8.8 μM; 2 mg/L) with the oxidizing agents hydrogen peroxide (HP; 0.25 mM) and persulfate (PS; 0.25 mM) activated using zero-valent aluminum (ZVA) nanoparticles (1 g/L) was investigated at a pH of 3. In the absence of the solutes, the PS/ZVA treatment system was superior to the HP/ZVA system in terms of BPA removal rates and kinetics. Further, the HP/ZVA process was not affected by nitrate (50 mg/L) addition, whereas chloride (250 mg/L) exhibited no effect on the PS/ZVA process. The negative effect of inorganic anions on BPA removal generally speaking increased with increasing charge in the following order: NO₃^? (no inhibition)?<?Cl^? (250 mg/L)?=?SO₄^2??<?PO₄^3? for HP/ZVA and Cl^? (250 mg/L; no inhibition)?<?NO₃^??<?SO₄^2??<?PO₄^3? for PS/ZVA. Upon addition of 20 mg/L humic acid representing natural organic matter, BPA removals decreased from 72 and 100% in the absence of solutes to 24 and 57% for HP/ZVA and PS/ZVA treatments, respectively. The solute mixture containing all inorganic and organic solutes together partly suppressed the inhibitory effects of phosphate and humic acid on BPA removals decreasing to 46 and 43% after HP/ZVA and PS/ZVA treatments, respectively. Dissolved organic carbon removals were obtained in the range of 30 and 47% (the HP/ZVA process), as well as 47 and 57% (the PS/ZVA process) for the experiments in the presence of 20 mg/L humic acid and solute mixture, respectively. The relative Vibrio fischeri photoluminescence inhibition decreased particularly for the PS/ZVA treatment system, which exhibited a higher treatment performance than the HP/ZVA treatment system.     

Maximum nitrogen removal in the step-feed activated sludge process.

This paper presents a mathematical framework that can be used to determine the flow distributions for a step-feed activated sludge process that result in maximum nitrogen removal. The model indicates that nitrogen removal efficiency in a step-feed activated sludge process is highly dependent on the ultimate biochemical oxygen demand (BOD(L))-to-total Kjeldahl nitrogen (TKN) ratio of the wastewater. For typical domestic wastewater, which has a relatively high BOD(L)-to-TKN ratio, the step-feed process will outperform the Modified Ludzack-Ettinger process for nitrogen removal, when the flow to each step is optimally distributed. Using plant-specific water quality data and operating conditions from a 1-year period, nitrogen removal performance for four step-feed activated sludge plants operated by the Sanitation Districts of Los Angeles County (California) was calculated using the developed model. The calculated nitrogen removal efficiencies match well with the actual plant performance data. These results validate the model as a useful tool for predicting nitrogen removal in a step-feed activated sludge process. Other analyses revealed that improvements in nitrogen removal at existing facilities are achievable by adjusting the split of primary effluent flow to each anoxic zone several times during the day. The timing of the adjustments and the optimal flow splits can be determined from data on diurnal fluctuations in BOD(L) and TKN concentrations. An example is provided to illustrate the application of such an operating strategy and the potential enhancement of nitrogen removal.     

氯化铁处理AB工艺二级出水中的磷

铁盐混凝剂因其高电荷、安全无毒、易于控制等优点,在城市污水厂除磷方面得到了进一步的发展和应用。为了考察FeCl3除磷的作用特征,探讨除磷效率随pH值、FeCl3投加量等混凝参数的变化规律,以氯化铁(FeCl3)为除磷剂,某城市污水处理厂二级出水为实验水样,进行了实验研究。研究结果表明,水样的硬度对混凝剂除磷性能有较大影响,在最佳工艺条件———不调节水样pH值、FeCl3投加量为75 mg/L时,可将废水中的总磷含量从4.95 mg/L降至0.44 mg/L以下,处理出水可达《城镇污水处理厂污染物排放标准》(GB 18918-2002)中的一级A排放标准(GB18918-2002)(TP<0.50 mg/L)。     

Removal of pyrene and benzo(a)pyrene from contaminated water by sequential and simultaneous ozonation and biotreatment.

The removal of pyrene and benzo(a)pyrene from contaminated water by sequential and simultaneous ozonation-bioremediation techniques was investigated. During the sequential treatment, ozonation using 0.5 or 2.5 mg/L ozone was used as a pretreatment process, whereas, during the simultaneous treatment process, ozonation of hydrocarbon-contaminated water at a predetermined duration using 0.5 mg/L ozone was made in the presence of microbial biomass. Ozonation was not beneficial for the removal of pyrene. However, despite a decreased specific biodegradation rate, ozonation improved the overall elimination of benzo(a)pyrene during both treatment processes. The overall removal of benzo(a)pyrene increased from 23 to 91% after exposure of the water to 0.5 mg/L ozone for 30 minutes during the simultaneous treatment process and further to 100% following exposure to 2.5 mg/L ozone for 60 minutes during the sequential treatment mode, demonstrating the benefits of combined ozonation-biological treatment for the removal of polycyclic aromatic hydrocarbons.     

化学生物絮凝与化学絮凝工艺处理城市污水--加药量对污染物去除效果的影响

化学生物絮凝工艺是利用将化学和生物协同絮凝作用处理污水的强化一级新工艺.试验通过在不同加药量情况下化学生物絮凝和化学絮凝工艺的中试试验对比研究,得出在相同加药量条件下,化学生物絮凝污染物去除效率均优于化学絮凝工艺10%～20%.在70 mg/L液体聚合氯化铝铁复配0.5 mg/L PAM的加药条件下,化学生物絮凝工艺经过30 min的水力停留时间,在进水CODCr为100～260 mg/L,TP为2～4 mg/L,SS为80～150 mg/L,NH3-N为10～25 mg/L条件下,出水CODCr、TP、SS、NH3-N满足城镇污水处理厂污染物排放二级标准.     

Biological assessment of bisphenol A degradation in water following direct photolysis and UV advanced oxidation

Endocrine disrupting compounds (EDCs) are exogenous environmental chemicals that can interfere with normal hormone function and present a potential threat to both environmental and human health. The fate, distribution and degradation of EDCs is a subject of considerable investigation. To date, several studies have demonstrated that conventional water treatment processes are ineffective for removal of most EDCs and in some instances produce multiple unknown transformation products. In this study we have investigated the use of direct photolysis with low-pressure (LP) Hg UV lamps and UV+hydrogen peroxide (H(2)O(2)) advanced oxidation process (AOP) for the degradation of a prototypic endocrine disrupter, bisphenol A (BPA), in laboratory water. Removal rates of BPA and formation of degradation products were determined by high performance liquid chromatography (HPLC) analysis. Changes in estrogenic activity were evaluated using both in vitro yeast estrogen screen (YES) and in vivo vitellogenin (VTG) assays with Japanese medaka fish (Oryzias latipes). Our results demonstrate that UV alone did not effectively degrade BPA. However, UV in combination with H(2)O(2) significantly removed BPA parent compound and aqueous estrogenic activity in vitro and in vivo. Removal rates of in vivo estrogenic activity were significantly lower than those observed in vitro, demonstrating differential sensitivities of these bioassays and that certain UV/AOP metabolites may retain estrogenic activity. Furthermore, the UV/H(2)O(2) AOP was effective for reducing larval lethality in treated BPA solutions, suggesting BPA degradation occurred and that the degradation process did not result in the production of acutely toxic intermediates.     

Solar CPC pilot plant photocatalytic degradation of bisphenol A in waters and wastewaters using suspended and supported-TiO2. Influence of photogenerated species

Photocatalytic degradation of bisphenol A (BPA) in waters and wastewaters in the presence of titanium dioxide (TiO₂) was performed under different conditions. Suspensions of the TiO₂ were used to compare the degradation efficiency of BPA (20 mg L^?1) in batch and compound parabolic collector (CPC) reactors. A TiO₂ catalyst supported on glass spheres was prepared (sol–gel method) and used in a CPC solar pilot plant for the photodegradation of BPA (100 μg L^?1). The influence of OH·, O₂ ^·?, and h ⁺ on the BPA degradation were evaluated. The radicals OH· and O₂ ^·? were proved to be the main species involved on BPA photodegradation. Total organic carbon (TOC) and carboxylic acids were determined to evaluate the BPA mineralization during the photodegradation process. Some toxicological effects of BPA and its photoproducts on Eisenia andrei earthworms were evaluated. The results show that the optimal concentration of suspended TiO₂ to degrade BPA in batch or CPC reactors was 0.1 g L^?1. According to biological tests, the BPA LC₅₀ in 24 h for E. andrei was of 1.7?×?10^?2 mg cm^?2. The photocatalytic degradation of BPA mediated by TiO₂ supported on glass spheres suffered strong influence of the water matrix. On real municipal wastewater treatment plant (MWWTP) secondary effluent, 30 % of BPA remains in solution; nevertheless, the method has the enormous advantage since it eliminates the need of catalyst removal step, reducing the cost of treatment.     

太阳能固定膜光催化去除双酚A的特性与效果

以太阳能固定膜光催化中试装置,研究了光解、初始浓度和平均光强等对双酚A(BPA)光催化去除的影响及BPA的矿化和在自来水中的处理效果.试验结果表明,BPA在日光照射下很难光解,其光催化降解呈表观一级反应,在平均光强介于5.7～23.5 W/m2时,表观反应速率常数和平均光强呈线性关系.太阳能光催化对BPA具有良好的矿化作用,但其降解与以UV254为光源的降解有不同的机理.太阳能光催化对自来水中BPA也具有较好的处理效果.     

混凝-超滤短流程工艺处理北方水库原水

采用混凝-超滤膜短流程工艺对大伙房水库原水进行处理，考察其除污染性能和膜污染情况，并对该短流程工艺参数进行优化。结果表明，当利用超滤膜直接过滤原水时，膜污染较重，并且对污染物质的去除率较低；而采用混凝．超滤短流程工艺时，膜污染得到一定程度上的缓解；当絮凝剂投加量为7mg／L、膜清洗周期为30min时，对浊度、CODMn和UV254的去除率分别为95．61％、40．42％和37．12％，出水水质能够满足生活饮用水卫生标准。     

超声波／零价铁降解水中双酚A

研究了超声波／零价铁（US／Fe^0）工艺对水中双酚A（BPA）的降解效果及影响因素。结果表明，US／Fe^0工艺可以有效降解水中的BPA，具有协同作用，且降解过程符合一级动力学规律；Fe^0具有促进和抑制的双重作用；超声功率越大，越有利于BPA的降解；初始浓度较低时，BPA的降解效果较好；弱酸性条件有利于BPA的降解；加入一定量的自由基捕获剂（正丁醇）可以抑制BPA的降解；联合作用2h后，TOC的去除率较低，说明其矿化程度不完全。     

混凝-超滤短流程工艺处理北方水库原水简

采用混凝-超滤膜短流程工艺对大伙房水库原水进行处理，考察其除污染性能和膜污染情况，并对该短流程工艺参数进行优化。结果表明，当利用超滤膜直接过滤原水时，膜污染较重，并且对污染物质的去除率较低；而采用混凝-超滤短流程工艺时，膜污染得到一定程度上的缓解；当絮凝剂投加量为7 mg/L、膜清洗周期为30 min时，对浊度、COD_Mn和UV₂₅₄的去除率分别为95.61%、40.42%和37.12%，出水水质能够满足生活饮用水卫生标准。     

日本净化槽技术在农村生活污水处理中的应用

引进日本净化槽技术在中国浙江农村污水处理中应用,探索净化槽技术在浙江农村地区的推广应用前景。膜式净化槽污水处理系统应用先进的浸没式平板膜组件,采用MBR工艺,实现对污水中有机物、氮和磷营养盐类的有效去除。正常工况条件下,监测结果表明,处理系统对COD、BOD5、氨氮、总磷和悬浮物的平均去除率分别为83.64%、84.46%、97.94%、94.13%和93.95%。膜式净化槽系统处理出水水质好且稳定,可直接回用,适宜对水质要求较高和经济条件较好的地区选用。今后在中国农村推广应用净化槽,需加强维护管理制度建设。     

Effect of copper(II) on natural organic matter removal during drinking water coagulation using aluminum-based coagulants.

Coagulation has been proposed as a best available technology for controlling natural organic matter (NOM) during drinking water treatment. The presence of heavy metals such as copper(II) in source water, which may form copper-NOM complexes and/or interact with a coagulant, may pose a potential challenge on the coagulation of NOM. In this work, the effect of copper(II) on NOM removal by coagulation using alum or PAX-18 (a commercial polymerized aluminum chloride from Kemiron Inc., Bartow, Florida) was examined. The results show that the presence of 1 to 10 mg/L of copper(H) in the simulated waters improved the total organic carbon (TOC) removal by up to 25% for alum coagulation and by up to 22% for PAX-18 coagulation. The increased NOM removal with the presence of copper(II) in the waters can most likely be ascribed to the formation copper-NOM complexes that may be more adsorbable on aluminum precipitates and to the formation of copper(II) co-precipitates that may also adsorb NOM. The presence of 1 to 5 mg/L of copper(I) in the waters containing 3 mg/L NOM as carbon was reduced below the maximum contaminant level goal (1.3 mg/L as copper) using either coagulant. The results suggest that the presence of copper(H) in source water may not adversely affect the NOM removal by coagulation. A good linear correlation was observed between the TOC removal efficiency and the log-total moles of the precipitated metals, which include the metal ion from a coagulant and the divalent metal ion(s) in source water.     

Comparisons of polychromatic and monochromatic UV-based treatments of bisphenol-A in water via toxicity assessments

Polychromatic ultraviolet irradiation, such as from medium pressure (MP) Hg lamps may enhance the UV degradation of environmental pollutants as compared to low pressure (LP) Hg UV sources emitting monochromatic irradiation. Typically, studies involving destruction of environmental pollutants such as endocrine disrupting compounds (EDCs) are based on measurement of the parent compound decay using analytical chemistry, but such information is insufficient to determine an effective treatment endpoint because the identity and biological activity of many transformation products remain unknown. Bioanalytical methods to assess residual biological activity of a treated water offers one means to compare removal efficiency of EDC activity between MP- and LP-UV lamps under photolysis and UV/H2O2 oxidation. In this study, changes in estrogenic activity of bisphenol-A (BPA) as a function of UV treatment were evaluated using both an in vitro yeast estrogen screen and in vivo vitellogenin assay with Japanese medaka (Oryzias latipes) fish. Decay of BPA parent compound and formation of degradation products were followed using HPLC analysis. Results demonstrated that MP-UV direct photolysis more effectively removed BPA and associated estrogenic activity compared to LP-UV lamps. UV in combination with H2O2 significantly removed estrogenic activity in vitro and in vivo compared to direct photolysis; however, no significant difference in removal rates was found between the two lamps under UV/H2O2 oxidation. Furthermore, the UV/H2O2 process was effective for reducing embryo toxicity of BPA, but resulted in the production of acidic intermediates, causing acute toxicity and delayed hatching in some medaka embryos.